CN114605353B - Preparation method of piperazine pyrophosphate - Google Patents
Preparation method of piperazine pyrophosphate Download PDFInfo
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- CN114605353B CN114605353B CN202210256080.1A CN202210256080A CN114605353B CN 114605353 B CN114605353 B CN 114605353B CN 202210256080 A CN202210256080 A CN 202210256080A CN 114605353 B CN114605353 B CN 114605353B
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- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 4
- 239000001177 diphosphate Substances 0.000 claims 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 1
- 235000011180 diphosphates Nutrition 0.000 claims 1
- 241001313857 Bletilla striata Species 0.000 abstract description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 25
- 229960005141 piperazine Drugs 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 125000004193 piperazinyl group Chemical group 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- -1 Piperazine phosphates Chemical class 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000277284 Salvelinus fontinalis Species 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
Abstract
The invention discloses a preparation method of a novel piperazine diphosphate, P 2 O 5 And calcium hydride as catalyst, and through catalytic condensation and dewatering to prepare piperazine pyrophosphate. The process is as follows: adding piperazine diphosphate and a small amount of catalyst into a kneader, introducing nitrogen for 30min to replace air in a reaction system, heating the materials to 180-230 ℃ to react for 2-7h, cooling to room temperature, and crushing by a universal crusher to obtain a crude product; and (3) stirring and washing the crude product with a certain amount of low-carbon alcohol which is easy to dissolve in water at room temperature for 0.5h, then vacuum filtering, washing a filter cake with a small amount of low-carbon alcohol, and drying the washed filter cake to constant weight at 100+/-10 ℃ to obtain the product. The piperazine pyrophosphate prepared by the method has the advantages of low condensation temperature, low product bletilla striata water solubility and the like.
Description
Technical Field
The invention relates to a preparation method of piperazine pyrophosphate, in particular to a method for preparing piperazine pyrophosphate by taking piperazine diphosphate as a raw material through catalytic condensation dehydration, belonging to the fields of fine chemical engineering and polymer material auxiliaries.
Background
Piperazine pyrophosphate (PPAP) is a novel phosphorus-nitrogen flame retardant developed in japan, and has the following structure:
there are several patents reporting the preparation methods of PPAP, which can be divided into the following three categories:
(1) Metathesis precipitation process
Sodium pyrophosphate and piperazine react in hydrochloric acid solution to generate water-insoluble PPAP, and the synthesis principle is as follows:
the patent (Rowton R.Piperazine phosphates as fire retardants for organic polymers:U.S. patent 3810850,1974-5-14) discloses the process of: the anhydrous piperazine and anhydrous sodium pyrophosphate react in hydrochloric acid solution, PPAP is difficult to dissolve in water to form precipitate, and PPAP products can be obtained after separation. A similar preparation method is disclosed in the patent (Marciandi F, binaghi M.Flameproof polymeric compositions containing acid piperazine pyrophosphate:U.S. patent 4599375,1986-7-8), which comprises the following steps: 750g of sodium pyrophosphate decahydrate was charged into a 5L reactor, fully dissolved with 2500mL of water and cooled to 10℃with an ice bath, and acidified with 563mL of 37% hydrochloric acid at a system temperature of not higher than 12 ℃. 149g of piperazine were dissolved in 625mL of water at about 22 ℃. Adding the acidified sodium pyrophosphate solution into piperazine solution, maintaining stirring for 2-3 h (the temperature is kept at about 7 ℃) after crystals are precipitated (the pH is 3-4), filtering, washing a filter cake with water, and drying in a vacuum drying oven at 105 ℃ for 6h to obtain 235g PPAP (the yield is 53%), wherein the thermal stability of the product is more than 280 ℃.
Sodium pyrophosphate has a low solubility in hydrochloric acid solution, and therefore, the concentration of reactants during the reaction is low, resulting in a low yield of the product.
(2) Phosphorus pentoxide process
Firstly, phosphorus pentoxide and phosphoric acid react to generate pyrophosphoric acid, and then the pyrophosphoric acid reacts with piperazine to generate PPAP, and the synthesis principle is as follows:
the method is due to P 2 O 5 The depolymerization degree is not easy to control, and the piperazine volatilizes and charres when the temperature is slightly high, so that the actual efficiency is lower. For this purpose, zhang Xiuqin (Zhang Xiuqin. A novel method for preparing piperazine pyrophosphate in high yield. Guangdong chemical industry, 2017,44 (15): 86-87) pair employs P 2 O 5 The method of synthesizing PPAP is improved. The technological process is as follows: first, equimolar ratio of P 2 O 5 And phosphoric acid is reacted for 1h at 200 ℃, then the temperature is reduced to 80 ℃, glacial acetic acid is added, stirring is carried out for 0.5h, then anhydrous piperazine is added, the temperature is increased to 120 ℃ for 2h, and the product is obtained, wherein the product yield is 96.5%. Glacial acetic acid is used as solvent, the materials are easy to disperse, the reaction temperature is low, and the formed product particles are not generatedSticky, thus the yield is greatly improved and the product is white in color. Glacial acetic acid is difficult to recover and corrodes equipment. In practice there is also P 2 O 5 The depolymerization degree is not easy to control.
(3) Piperazine diphosphate condensation process
The method is to prepare the piperazine diphosphate by reacting phosphoric acid and piperazine, and then dehydrate to prepare PPAP, wherein the reaction principle is as follows:
xu et al (Xu M J, cia S Y, liu C, et al preparation of Poly (phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy resin Journal of Polymer Science,2018,36 (5): 1-10) synthesized PPAP using this method. Firstly, 85% of phosphoric acid and piperazine react for 2 hours at 85 ℃ according to the mol ratio of 2:1 to obtain piperazine diphosphate, then the piperazine diphosphate is put into a tube furnace, and dehydrated and polycondensed for 40 minutes at 230 ℃ in nitrogen atmosphere to obtain the product, wherein the total yield of the product is 92.1%.
Liu Chuan et al (Liu Chuan, xu Miaojun. Application study of piperazine pyrophosphate/melamine flame retardant epoxy resin. Plastics science, 2017,45 (4): 113-116), tang Haishan (Tang Haishan. Synthesis of piperazine phosphate and application study in flame retardant polypropylene. University of east China university paper, 2015) and Yang Youjiang et al (Yang Youjiang, yuan Zhimin, ginger new, et al) PPAP was also synthesized by this method, and similar results were obtained.
The method has the advantages of high yield, cheap raw materials, simple process, and high polycondensation temperature, so that the color of the product is easy to blacken. How to reduce the polycondensation temperature to obtain a product with high whiteness is a problem to be solved by the method.
By comprehensively comparing the schemes, the piperazine diphosphate condensation method is an ideal method, and the key is how to reduce the condensation temperature and improve the color of the product.
Disclosure of Invention
In the dyeing process of the phosphonic acid type reactive dye, dicyandiamide is usually used as a catalyst, the phosphonic acid group is catalyzed to be dehydrated into the bisphosphonic acid anhydride, and then the bisphosphonic acid anhydride is esterified with hydroxyl groups on the fiber to dye the fiber. Calcium hydride and P 2 O 5 Are all efficient dehydrating agents. Urea is commonly used for the condensation dehydration of various ammonium phosphates to ammonium polyphosphate. Accordingly, the applicant of this patent is directed to the use of dicyandiamide, urea, calcium hydride and P 2 O 5 Experiments were performed for dehydration catalysts to find P 2 O 5 And calcium hydride has good catalytic effect on the condensation of piperazine diphosphate.
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: adding piperazine diphosphate and a small amount of catalyst into a kneader, introducing nitrogen for 30min to replace air in a reaction system, heating the materials to 180-230 ℃ to react for 2-7h, cooling to room temperature, and crushing by a universal crusher to obtain a crude product;
(2) Purifying: adding the crude product and a certain amount of low-carbon alcohol which is easy to dissolve in water into a stirring device, stirring and washing for 0.5h at room temperature, then vacuum filtering, washing a filter cake with a small amount of low-carbon alcohol, and drying the washed filter cake to constant weight at 100+/-10 ℃ to obtain the product.
Further, the catalyst is P 2 O 5 And a mixture of calcium hydride in a mass ratio of 1:0.0 to 1.0, preferably 1:0.2 to 0.6;
the mass ratio of the piperazine diphosphate to the catalyst is 1:0.010-0.018, preferably 1:0.012-0.015;
the lower alcohol is methanol, ethanol, propanol and isopropanol, preferably methanol. The mass ratio of the crude product to the lower alcohol is 1:1.0-2.0, preferably 1:1.2-1.5, wherein the lower alcohol for stirring and washing is 2/3 of the total amount of the lower alcohol, and the lower alcohol for washing the filter cake is 1/3 of the total amount of the lower alcohol.
In the preparation method, the catalyst is adopted to obviously reduce the condensation temperature of the piperazine diphosphate, and the low-carbon alcohol is adopted for washing and purifying to obviously improve the color of the product and reduce the water solubility of the product. Therefore, the piperazine pyrophosphate prepared by the method has the advantages of low condensation temperature, low product bletilla striata water solubility and the like.
Drawings
FIG. 1 is an infrared spectrum of piperazine pyrophosphate obtained in example 1 of the present invention;
FIG. 2 shows the solid nuclear magnetic resonance spectrum (solid) of piperazine pyrophosphate obtained in example 1 of the present invention 31 P NMR)；
FIG. 3 shows the solid nuclear magnetic carbon spectrum (solid) of piperazine pyrophosphate obtained in example 1 of the present invention 13 C NMR)。
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
The percentages used in the present invention are mass percentages unless otherwise indicated.
The infrared spectrum of the product was determined using a TENSOR-27 infrared spectrometer from Bruce, germany. The method is a tabletting method, and the scanning range is 400-4000 cm -1 。
Solid body 13 C NMR 31 P NMR was measured by Bruker AVANCE III HD 400MHz nuclear magnetic resonance apparatus manufactured by Bruker corporation, switzerland. Solid body 31 P NMR test conditions: H/X dual resonance solid probe: 4mm; the rotating speed is 12kHz; detecting resonance frequency as 161.98MHz; sampling time is 5.12 mu s; the spectrum width is 80kHz; the cycle delay time is 6.25 mu s; the scanning times are 1025 times/h. Solid body 13 C NMR test conditions: H/X dual resonance solid probe: 4mm; the rotating speed is 5kHz; the detection resonance frequency is 100.625MHz; sampling time is 5.12 mu s; the spectral width is 50kHz; the cycle delay time is 6.5 mu s; the number of scans was 4096/h.
Phosphoric acid, calcium hydride and P used 2 O 5 All are analytically pure reagents produced by the company of national pharmaceutical group chemical reagent, and piperazine is a product of the company of Changzhou Ningding chemical Co.
Example 1
The synthesis of piperazine diphosphate comprises the following specific steps:
800mL of deionized water and 861.4g (10 mol) of anhydrous piperazine are added into a 5L reaction kettle provided with a stirrer, a thermometer, a condenser and a dropping funnel, the mixture is heated to about 40 ℃, 2306g (20.0 mol) of 85% phosphoric acid is added dropwise after the mixture is completely dissolved by stirring, the mixture is completely dissolved for about 1 hour, the mixture is heated to 85+/-5 ℃ for 2 hours, then the mixture is cooled to room temperature and filtered, a filter cake is washed 3 times by deionized ice water, 600mL of water is used each time, and finally the washed filter cake is dried to constant weight at 100+/-10 ℃ to obtain 2404g (the theoretical yield is 2821.4 g) of the product, and the yield is 85.2%.
Example 2
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate and 20g P 2 O 5 And 4g of calcium hydride are added into a 5L kneader, nitrogen is firstly introduced for 30min, then the materials are heated to 210+/-5 ℃ through an oil bath for reaction for 5h, then the temperature is reduced to room temperature, and 1900g of crude product is obtained by crushing through a universal crusher. The crude product had a water solubility of 0.35g/100mL water and a light gray color.
(2) Purifying: 1900g of the crude product and 1900g of methanol are added into a 5L stirring device, stirred and washed for 0.5h at room temperature, then vacuum filtration is carried out, a filter cake is washed by 950g of methanol, and the washed filter cake is dried to constant weight at 100+/-10 ℃ to obtain 1790g of white powdery product. The water solubility of the product was 0.15g/100mL of water.
The invention uses infrared spectrum and solid 31 PNMR and solids 13 C NMR measurement the product obtained in this example was structurally characterized. FIG. 1 shows the infrared spectrum (σ, cm) of piperazine pyrophosphate obtained in this example -1 ) The method comprises the steps of carrying out a first treatment on the surface of the FIG. 2 shows the piperazine pyrophosphate solid obtained in this example 31 PNMR; FIG. 3 shows the solid piperazine pyrophosphate obtained in this example 13 C NMR。
In fig. 1: 3399.22 and 3051.44cm -1 Is the stretching vibration peak of the N-H group on the piperazine ring; 2695.07cm -1 Is NH 2 + The N-H stretching vibration absorption peak; 1679.57cm -1 Is the bending vibration peak of the N-H group on the piperazine ring; 1514.27cm -1 Is piperazine ring-CH 2 -a bending vibration absorption peak; 1154.49cm -1 A telescopic vibration absorption peak for p=o bond; 1068cm -1 Is the telescopic vibration absorption peak of C-N group on piperazine ring; 980.67cm -1 Is the telescopic vibration absorption peak of P-O-P.
In FIG. 2, 3 distinct peaks are shown, 1.55ppm, -6.24ppm and-10.07 ppm, respectively, wherein 1.55ppm is the P peak of the terminal group in piperazine pyrophosphate, -6.24ppm and-10.07 ppm is the double peak generated by cleavage of the P element in the P-O-P group in piperazine pyrophosphate.
In FIG. 3, 37.35ppm is the C atom peak on the piperazine ring, indicating that the product contains a piperazine ring. Only one carbon peak is shown in the graph, which indicates that the purity of the product is higher.
The coincidence of the above infrared spectrum, nuclear magnetic resonance phosphorus spectrum and nuclear magnetic resonance carbon spectrum with piperazine pyrophosphate proves that the synthesized sample is piperazine pyrophosphate.
Example 3
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate and 20g P 2 O 5 And 6g of calcium hydride were charged into a 5L kneader, nitrogen was introduced for 30 minutes, and then the mixture was heated to 210.+ -. 5 ℃ by an oil bath for reaction for 5 hours, and then cooled to room temperature, and pulverized with a universal pulverizer to obtain 1901g of a crude product. The crude product had a water solubility of 0.36g/100mL water and a light gray color.
(2) Purifying: 1901g of crude product and 1900g of methanol are added into a 5L stirring device, stirred and washed for 0.5h at room temperature, then vacuum filtration is carried out, filter cakes are washed by 950g of methanol, and the washed filter cakes are dried to constant weight at 100+/-10 ℃ to obtain 1791g of white powdery product. The water solubility of the product was 0.15g/100mL of water.
In this example, the structural characterization of the obtained product was performed according to the method of example 2, and it was confirmed that the synthesized sample was the target product.
Example 4
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate and 22g P 2 O 5 And 4g of calcium hydride were charged into a 5L kneader, nitrogen was first introduced for 30 minutes, and then the mass was fed through an oil bathAfter heating to 210.+ -. 5 ℃ for 5 hours, the reaction was cooled to room temperature and crushed by a universal crusher to obtain 1898g of crude product. The crude product had a water solubility of 0.33g/100mL water and a light gray color.
(2) Purifying: 1898g of crude product and 1900g of ethanol are added into a 5L stirring device, stirred and washed for 0.5h at room temperature, then vacuum filtered, filter cake is washed by 950g of ethanol, and the washed filter cake is dried to constant weight at 100+/-10 ℃ to obtain 1792g of white powdery product. The water solubility of the product was 0.14g/100mL of water.
In this example, the structural characterization of the obtained product was performed according to the method of example 2, and it was confirmed that the synthesized sample was the target product.
Example 5
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate and 20g P 2 O 5 And 4g of calcium hydride are added into a 5L kneader, nitrogen is firstly introduced for 30min, then the materials are heated to 200+/-5 ℃ through an oil bath for reaction for 5h, then the temperature is reduced to room temperature, and 1906g of crude product is obtained by crushing through a universal crusher. The crude product had a water solubility of 0.45g/100mL water and a light gray color.
(2) Purifying: 1906g of crude product and 1900g of methanol are added into a 5L stirring device, stirred and washed for 0.5h at room temperature, then vacuum filtration is carried out, filter cakes are washed by 950g of methanol, and the washed filter cakes are dried to constant weight at 100+/-10 ℃ to obtain 1780g of white powdery product. The water solubility of the product was 0.25g/100mL of water.
In this example, the structural characterization of the obtained product was performed according to the method of example 2, and it was confirmed that the synthesized sample was the target product.
Example 6
The preparation process of piperazine pyrophosphate includes the following steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate and 20g P 2 O 5 And 4g of calcium hydride are added into a 5L kneader, nitrogen is firstly introduced for 30min, then the materials are heated to 220+/-5 ℃ through an oil bath for reaction for 5h, then the temperature is reduced to room temperature, and 1895g of crude product is obtained by crushing through a universal crusher. The water solubility of the crude product was 0.31g/100mL of water, the color was gray.
(2) Purifying: 1895g of the crude product and 1900g of methanol were introduced into a 5L stirring apparatus, washed at room temperature for 0.5h with stirring, followed by vacuum filtration, the filter cake was washed with 950g of methanol, and the washed filter cake was dried at 100.+ -. 10 ℃ to constant weight to give 1789g of a nearly white powdery product. The water solubility of the product was 0.15g/100mL of water.
In this example, the structural characterization of the obtained product was performed according to the method of example 2, and it was confirmed that the synthesized sample was the target product.
Comparative example 1
Compared with the preparation method, the preparation method does not add a catalyst and comprises the following specific steps:
(1) And (3) synthesis: 2000g of piperazine diphosphate is added into a 5L kneader, nitrogen is firstly introduced for 30min, the materials are heated to 230+/-5 ℃ through an oil bath and then react for 5h, then the temperature is reduced to room temperature, and 1902g of crude product is obtained by crushing through a universal crusher. The crude product had a water solubility of 0.45g/100mL water and a dark gray color.
(2) Purifying: 1902g of crude product and 1900g of methanol are added into a 5L stirring device, stirred and washed for 0.5h at room temperature, then vacuum filtered, filter cake is washed by 950g of ethanol, and the washed filter cake is dried to constant weight at 100+/-10 ℃ to obtain 1791g of light gray powdery product. The water solubility of the product was 0.16g/100mL of water.
The color of the product of the comparative example was significantly darker.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of piperazine pyrophosphate is characterized in thatPiperazine diphosphate is used as raw material, P 2 O 5 And calcium hydride as catalyst, and through catalytic condensation and dehydration to prepare piperazine pyrophosphate, the process is as follows: adding piperazine diphosphate and a catalyst into a kneader, introducing nitrogen for 30min to replace air in a reaction system, heating the materials to 180-220 ℃ to react for 2-7h, cooling to room temperature, and crushing by a universal crusher to obtain a crude product; adding the crude product and a certain amount of low-carbon alcohol which is easy to dissolve in water into a stirring device, stirring and washing for 0.5h at room temperature, then vacuum filtering, washing a filter cake with a small amount of low-carbon alcohol, and drying the washed filter cake to constant weight at 100+/-10 ℃ to obtain a product; the catalyst is P 2 O 5 And a mixture of calcium hydride in a mass ratio of 1:0.2-0.6.
2. The preparation method according to claim 1, wherein the mass ratio of the piperazine diphosphate to the catalyst is 1:0.010-0.018.
3. The method according to claim 1, wherein the lower alcohols are methanol, ethanol, propanol and isopropanol, the mass ratio of the crude product to the lower alcohols is 1:1.0-2.0, wherein the lower alcohols for stirring and washing are 2/3 of the total mass of the lower alcohols, and the cake washing is 1/3 of the total mass.
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| CN1845913A (en) * | 2003-10-16 | 2006-10-11 | 旭电化工业株式会社 | High-purity piperazine pyrophosphate and method for producing same |
| CN102482239A (en) * | 2009-08-20 | 2012-05-30 | 堺化学工业株式会社 | (poly) piperazine pyrophosphate powder and manufacturing method therefor |
| JP2014012704A (en) * | 2013-08-27 | 2014-01-23 | Adeka Corp | Flame-retardant synthetic resin composition |
| CN103992293A (en) * | 2014-05-07 | 2014-08-20 | 金发科技股份有限公司 | Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof |
| CN112778237A (en) * | 2020-12-31 | 2021-05-11 | 广州大学 | Synthesis method of piperazine pyrophosphate metal salt |
| CN113896693A (en) * | 2021-09-08 | 2022-01-07 | 云南云天化股份有限公司 | Preparation method of polyphosphoric acid piperazine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1845913A (en) * | 2003-10-16 | 2006-10-11 | 旭电化工业株式会社 | High-purity piperazine pyrophosphate and method for producing same |
| CN102482239A (en) * | 2009-08-20 | 2012-05-30 | 堺化学工业株式会社 | (poly) piperazine pyrophosphate powder and manufacturing method therefor |
| JP2014012704A (en) * | 2013-08-27 | 2014-01-23 | Adeka Corp | Flame-retardant synthetic resin composition |
| CN103992293A (en) * | 2014-05-07 | 2014-08-20 | 金发科技股份有限公司 | Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof |
| CN112778237A (en) * | 2020-12-31 | 2021-05-11 | 广州大学 | Synthesis method of piperazine pyrophosphate metal salt |
| CN113896693A (en) * | 2021-09-08 | 2022-01-07 | 云南云天化股份有限公司 | Preparation method of polyphosphoric acid piperazine |
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